Perfume compositions containing an alkyl cyclododeca-ketone

ABSTRACT

Fragrance materials prepared by acylation of trimethyl cyclododecatriene, processes for producing same, and perfume compositions containing such materials.

nits States Patent 1191 Hall June 11, 1974 PERFUNE COMPOSITIONS CONTAINING [58] Field of Search 252/522 AN ALKYL CYCLODODECA-KETONE 75 Inventor: John B. Hall, Rumson, NJ. [561 References CM [73] Assignee: International Flavors & Fragrances 3 235 601 37:25 PIATENTS 252/522 arsons C a New York 3,318,945 5/1967 Erman 252/522 [22] Filed: May 23, 1972 3,718,697 2/1973 Lemberg 252/522 Appl' No; 245388 Primary Examiner-Sam Rosen Related US. Application Data [60] Dii/ision of Ser. No. 752,145, Aug. 13, 1968, Pat. No. [57] ABSTRACT 3,754,036, which is a continuation-in-part of Set. No. Fragrance materials prepared by acylation of trimeth 1 Y Sept 1967 abandoned cyclododecatriene, processes for producing same, and l 52] U S C} 2525 perfume compositions containing such materials. [51] Int. Cl C1 lb 9/00 8 Claims, 8 Drawing Figures PATEWEMM 1 m4 SHEETSUF 5.

omw Ooh Obs w v m N .008 oomuooom vooow knQq Q Q towauwom totkmommY Qwwwwhg mma'asyy i CONT 2| 2| G AN ALKYL CYCLODODECA-KETONE This application is a division of Ser. No. 752,145 filed Aug. 13, 1968 now US. Pat. No. 3,754,036 which in turn is a continuation-in-part of application Ser. No. 667,398, filed Sept. 13, 1967, now abandoned.

BACKGROUND OF THE INVENTION THE INVENTION The invention comprises the novel compositions and component mixtures comprised in such compositions, as well as the novel processes and steps of processes according to which such compositions may be manufactured, specific embodiments of which are described hereinafter by way of example only and in accordance with what is now considered the preferred manner of practicing the invention.

Briefly, the perfume materials of this invention are ketones produced by acylating trialkyl cyclododecenes and recovering the acylated product. The products produced by these processes are suitable for incorporation into a wide variety of perfume and fragrance-modifying compositions, and such perfume and fragrancemodifying compositions are also contemplated herein.

It has been found that the novel materials of this invention have a persistent fragrance, as more fully described below, which particularly adapts them for incorporation into perfume compositions and fragrancemodifying compositions having a desirable woodyamber fragrance note. It will be appreciated by those skilled in the art from the present disclosure that the fragrance character can be varied according to the reaction conditions and the subsequent treatment of the materials produced in the reaction.

The present invention is further illustrated by the accompanying drawings wherein:

FIG. 1 is an infrared absorption (IR) spectrum of a novel acylated ketonic material and FIG. 2 is a nuclear magnetic resonance (NMR) spectrum of the same material;

FIGS. 3, 4, 5, 7 and 8 are IR spectra of hydrogenated materials according to this invention, and

FIG. 6 is an IR spectrum of a novel isomerized material.

The cyclic hydrocarbons treated according to this invention are trialkyl-substituted cyclododecenes, preferably such cyclododecenes having from one to three unsaturated carbon-to-carbon bonds. The lower alkyl groups having from one to three carbon atoms are contemplated, and the preferred alkyl substituent is methyl. The substances produced by trimerizing such methyl butadienes as isoprene, piperylene (1,3- pentadiene) or mixtures of isoprene and piperylene to obtain cyclic derivatives are a convenient source of such materials. Thus, cyclododecenes for use in the practice of this invention include 1,5,9-trimethyl cyclododecatrienel ,5,9; l ,5 ,9-trimethyl cyclododecatriene-l,5,l0; and other such trimethyl cyclododecatrienes.

Monoand diand trienoic cyclododecenes can be used, and it will be appreciated that, when the starting material is the triene obtained from the trimerization of polyenoic hydrocarbons, the monoand diunsaturated materials can be obtained by hydrogenating the triene. The acylated cyclododecene produced according to this invention can also be hydrogenated if a lower degree of unsaturation is desired. The cyclododecene starting material is generally a mixture of various cistrans isomers, and the several isomers have been found satisfactory in the practice of this invention.

It has been found that better results are obtained when the cyclododecene is of at least percent purity. When a relatively crude material is used, it can be puritied to the desired degree by convention techniques such as distillation, extraction, and the like. It will be understood that the positions of the alkyl substituents on, and the positions of the double bonds in, the cyclododecene ring can vary according to the starting material and mode of preparation of the cyclododecene.

The acylating agent used in the practice of the invention can be any material capable of adding the desired acyl group to the ring. Carboxylic acid anhydrides, such as propionic and butyric anhydrides, are desirable acylating agents. A preferred acylating agent in the present invention is acetic anhydride. Acylating agents such as acyl halides, as for example, acetyl chloride may be used. Still other equivalent materials will readily occur to those skilled in the art.

The acylation can be carried out in the presence of a solvent or other vehicle. The vehicle, if used, can be a liquid which is inert to the reactants, catalyst (as disclosed further below), and any other modifying materials present in the reaction mass. Thus, hydrocarbons and chlorinated hydrocarbons are useful as vehicles in the invention. The hydrocarbons and chlorinated hydrocarbons are preferably saturated. Methylene chloride is a desirable vehicle in the practice of the invention.

The acylation can be carried out with an excess of acetic anhydride which performs the function of a vehicle in the reaction mass, although a substantial excess of the anhydride may cause a high degree of polyacylation. In order to minimize such polyacylation, an excess of the trialkyl cyclododecene can be used in the reac-' tion mixture.

The reaction is preferably carried out in the presence of an acidic catalyst. It has been found that Friedel- Crafts acylation agents are especially desirable as catalysts. Thus, boron trifluoride, stannic chloride, ferric chloride, and zinc chloride are preferred catalysts. It will be understood that materials providing such catalysts under the reaction conditions can be used. For example, boron trifluoride-ether complex or boron trifluoride-acetic acid complex can be used.

When a strong Friedel-Crafts acylation agent is used as a catalyst, a lower reaction temperature is desirable to facilitate .control of the reaction velocity. When weaker F riedel-Crafts materials are used, a higher temperature is-convenient and desirable to achieve a conveniently rapid reaction rate. The reaction is accordingly carried out at temperatures ranging from below about 5C to about 100C, and the range of from about 5C to about 70C is preferred. Thus, with boron trifluoride an ice bath at 0C can be used, and with stannic or ferric chloride temperatures on the order of l0C-50C are desirable Zinc chloride gives good results at temperatures of about 70C.

The concentration of the catalyst can be varied from catalytic amounts, i.e., one or two percent of the cyclododecenes, up to molar amounts. Stronger catalysts such as boron trifluoride can be used in lower concentrations, whereas it is generally advantageous to use higher concentrations of the weaker catalysts such as zinc chloride.

The times required will vary with the temperatures, concentrations of reactants and catalyst, and the particular reactants and catalyst used. The times utilized in the reaction vary from that sufficient to obtain a homogeneous mixture of the reaction mass to several hours, although this can be varied even more widely by controlling the reaction temperature, reaction materials, vehicles, and catalysts, as disclosed above. Thus, times preferably range from about one-half hour to about hours.

The reaction can be carried out at sub-or superatmospheric pressure. This will vary according to the added vehicle, if any, contained in the reaction mixture, the acylating agent, and the temperature, and it is generally preferred that the reaction be carried out at substantially atmospheric pressure.

After the reaction has been completed or carried out to the extent desired, the acylated product is separated from the reaction mass. A preferred step in purification is removal of catalyst from the system by means of treatment with a suitable basic material. The basic material can either be a relatively strong one such as sodium hydroxide, or it can be a relatively weaker one, for example, the salt of a strong base and weaker acid, such as sodium carbonate, sodium acetate, and the like.

After catalyst removal, as described above, the reaction mass can be extracted to concentrate the desired products and/or it can be distilled. The partially purified material in a preferred aspect of the invention is then further purified by fractional distillation. If desired, other or further purification can be carried out by preparative chromatographic techniques.

As noted above, the reaction mass contains a number of materials, and it is preferred to purify it prior to use in-fragrance, perfume, and fragrance-modifying compositions. For many purposes it is desirable to have more highly purified materials which are substantially single substances or a mixture of closely related materials.

Efficacious materials according to the present invention include monocyclic alkyl ketones having the formula is it.

CH: CH:

wherein the dashed line is a single or a double bond and no more than one of the wavy lines is a double bond.

In the foregoing formula, A represents R represents a lower alkyl having up to about six carbon atoms and is preferably methyl or ethyl. In the formula for A given above, no more than one carbon-tocarbon double bond is present so that no more than one of the dashed lines represents a carbon-to-carbon double bond, and the other two represent single bonds. Accordingly, in the formula given above for A, m is 0 or l,n is l or 2,pis 2or 3, andm+n+pequals 5. It will be understood that the structural formulas herein represent cis and trans isomers of the novel ketones, as well as stereoisomers.

In one aspect of the present invention materials represented by the following structural formula are obtained:

C 3 CH3 This liquid has a camphor woody-amber fragrance note. According to mass spectroscopy, the liquid has a molecular weight of 246 (parent ion peak), a base peak m/e of 43 for bands at 1,660 and 830 cm, and a -C-CH band at the IR spectrum is as shown in FlGl 3. The spectrum 1,350 cm". The NMR spectrum shows shflvsa "W 5 \C=O No. of Assignment Chemical shift (p.p.m.) protons C=H (mult p 3 at -l a H wwaa ,1

C-CHz- 2.17, 2.00 (broad singlets) 9 (9.3) band at 1755 cm, and OHS-0:0 1.97 (singlet) r C-CH3 1.67-1.41 11 10.9)

I bands at 1670 and 830 cm'. Closely related materials found in admixture with the si ilar dihydro acylates can be prepared by initially foregoing mixture are represented by the structural formonohydrogenating h h d b i h l muia 7 V fl clododecatriene, and then acylating the hydrogenated material in accordance with the acylation procedure described above. Examples of the dihydro acylates thus cmc=0 on, produced are:

0 0 CH; CH: l A

on, on, H,oom The trimethyl acylate can be hydrogenated to reduce one, two, or three of the double bonds. Exemplary cm Cm Cm structural formulas for the dihydro (monohya drogenated) acylates are 0 0 Bio-ii -cm Hie-ii on,

cmo=o cm CH3C=0 on,

on, cm 0H, CH;

T CH: CH: CH: CH: 0 and 3 CH;

CH: CH:

cm cm w W The woody-amber odor of this liquid is similar to that The woody amber odor of this liquid is similar to that of the unhydrogenated acylates described above, and of the monohydrogenated acylate described above, and

the IR spectrum as obtained on a Perkin-Elmer Model 21 instrument is shown in FIG. 7. The spectrum shows band at 1712 cm, a

band at 1,7565,

H C=J] bands at 1,670 and 832 cm", and =CH bands at 3,080, 1,645 and 895 cm.

The tetrahydro acylate is obtained either directly by hydrogenation of the acylate or by hydrogenation of the dihydro acylate (formed by hydrogenating the acylate.) The tetrahydro acylates thus formed are represented by the following structures This liquid has a shaded camphor woody-amber fragrance note and the IR spectrum shown in FIG. 4. This IR spectrum discloses a band at 1,710 cm", a

band at 1,755 cm, and

bands at 1,670 and 830 cm".

Similar tetrahydro acylates can be prepared by initially dihydrogenating the hydrocarbon and then acylating in accordance with the acylation procedure described hereinabove. Examples of the tetrahydro acylates thus produced are:

0 Inc-ii on,

cfi, cm

0 Biol: cm

ofi, CH;

The woody, amber odor of this liquid is similar to that of the dihydrogenated acylate described above, and the IR spectrum as obtained on a Perkin-Elmer Model 21 instrument is shown in FIG. 8. This spectrum shows a band at 1,712 cmfi a band at 1,755 cm,

bands at 1,670 and 832 cm and =CH bands at 3,080, 1,645, and 895 cm".

Further hydrogenation of the carbon-to-carbon double bond of the tetrahydro material or complete hydrogenation of the carbon-to-carbon unsaturation in the original acylate provides hexahydro acylates having the structural formula C 3 CH3 The hydrogenated liquid has a shaded woody-amber fragrance and the IR spectrum depicted in FIG. 5. This spectrum shows a band at 1,710 cm and a band at 1,755 cm. I

Hydrogenation to prepare the dihydro, tetrahydro, and hexahydro acylates is carried out by adding the desired number of moles of hydrogen under pressure in the presence of a hydrogenation catalyst. Pressures ranging from atmospheric up to about 500 psig can be CH3 CH:

CH C=O CH CH1 2 a CH; OH;

This is a liquid having a'iid' lrifier fragrance note and exhibiting IR absorption bands for at 1,112 cm, and =CH at 3,080, 1,645 and 890 4 cm. This material can be hydrogenated as disclosed above or isomerized as disclosed hereinafter.

A conjugated ketone can be produced from the acylate by treatment of the latter with an isomerization agent such as an alcoholic alkali-metal alkanoate under anhydrous conditions. For example, the reaction may be carried out with sodium methylate in anhydrous methanol. The reaction is generally carried out at temperatures of about 70C.

Thus, treatment of the acylate prepared with acetic anhydride will provide an isomerized mixture of materials having a boiling point of l l7l 23C at 0.6 mm Hg and one component of which is represented by the following structural formula:

CHJ CHa Model 21 instrument. This spectrum shows bands for at 1,710 cm,

at 1,350 cm",

H A at 830 cm, and conjugated at 1,690 cm". This material can be hydrogenated with one, two or three moles of hydrogen in accordance with the foregoing procedures to yield the dihydro, tetrahydro, or hexahydro derivatives.

Acylation of the trimethyl cyclododecatriene derived by trimerizing a mixture of isoprene and piperylene provides a product boiling at 84-93C at 1.4 mm Hg which comprises a component having the structural formula:

CH1 C=0 CH2 CH: CH;

and a component having the stru cfifral formula: v v

7 WW-'7 or1=c=0 CH3 0 agents and can be incorporated into a wide variety of compositions which will be enhanced by the woody fragrance note of the trialkyl cyclododecene acylate. It has been found that the products of this invention are especially desirable due to their persistence which, in'

many cases, lasts for periods of weeks under actual use conditions. The materials produced according to this invention can be added to perfume compositions in their pure form or as mixtures of materials in fragranceimparting compositions to give a desired fragrance character to a finished perfume material. The perfume and fragrance compositions of this invention are suitable in a wide variety of perfumed materials and can be also used to enhance, modify, or reinforce natural fragrance materials.

Thus, the acylated cyclic materials of this invention are useful as olfactory agents and fragrances. As disclosed above, the products may be employed in admixture with their isomers as obtained from the reaction mixture or the individual components may be employed alone. The acylated materials contribute a camphoraceous woody-amber odor.

The term perfume composition is used herein to mean a mixture of compounds, including, for example, natural oils, synthetic oils, alcohols, aldehydes, ketones, esters, lactones, and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain: (a) the main note or the bouquet or foundationstone of the composition; (b) modifiers which roundoff and accompany the main note; fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and (d) top-notes which are usually low-boiling fresh-smelling materials. Such perfume compositions orthe novel materials of this invention can be used in conjunction with carriers, vehicles, solvents, dispersants, emulsifiers, surface-active agents, aerosol propellants, and the like.

In perfume compositions the individual components contribute their particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effect of each ingredient. Thus, the individual compounds of this invention, or mixtures thereof may be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of mixtures or compounds of this invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 3.0 percent by weight of mixtures or compounds of this invention, or even less can be used to impart a woody-amber odor to soaps, cosmetics and other products. The amount employed will depend on considerations of cost, nature of the end product, the effect desired in the finished product, and the particular fragrance sought.

The materials disclosed herein can be used alone, in a fragrance-modifying composition, or in a perfume composition as olfactory components in detergents and soaps; space deodorants; perfumes; colognes; bath preparations such as bath oil, bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, sun .screens; powders such as talcs, dusting powders, face powder, and the like.

The following examples serve to illustrate embodiments of the invention as it is now preferred to practice it. It will be understood that these examples are illustrative and the invention is to be considered restricted thereto only as indicated in the appended claims.

EXAMPLE I Into a -liter reaction flask equipped-with a stirrer, thermometer, reflux condenser, addition funnel and drying tube are charged the following materials:

1,250 ml Acetic anhydride 1,550 ml BF -etherate 500 g. Liglg'rnethyl cyclododecatriene-1,5,9, as

described below.

The flask is charged initially with acetic anhydride and BF -etherate and then cooled to 0C. At 0C, the trimethyl cyclododecatriene is added. The reaction mass is stirred and made homogeneous, and is then poured onto 4,000 g. of ice. Thereafter, sodium hydroxide (5 percent aqueous) is added to neutralize the mass. The two resulting phases are separated, and the aqueous phase is extracted with benzene. The benzene extract is bulked with the main organic phase, and the benzene solvent is then stripped off. The weight of the resulting oil is 645 g. The oil is then distilled. The ketonic product thus obtained has a boiling range of 180-210C at 2 mm Hg and a persistent woody-amber fragrance.

EXAMPLE II Into a 500 ml reaction flask equipped with a stirrer, thermometer, reflux condenser and addition funnel are added the following:

g. Methylene chloride (CI-I Cl 100 g. 1,5,9-Trimethyl cyclododecatriene-1,5,9

10 g. Stannic chloride 60 g. Acetic anhydride.

The methylene chloride and trimethyl cyclododecatriene are initially placed into the flask. Then the stannic chloride is added at temperatures between 25 and 30C. Immediately subsequent to the stannic chloride addition, acetic anhydride is added at temperatures between 20 and 30C. The reaction is then allowed to proceed for a period of two hours between temperatures of 22 and 28C.

At the end of the 2-hour period, the reaction mass is worked-up. One hundred ml of benzene is added to the mass, and the mass is then washed with one volume of sodium chloride solution, whereupon two phases are formed. 'The organic phase is separated and washed with one volume of 5 percent sodium bicarbonate and then with one volume of 10 percent sodium chloride solution. The benzene is stripped out of the organic phase. The net weight of the resulting ketonic product prior to distillation is 83.0 g.

After distillation, the preferred material has a boiling point of 126134C at 1 mm Hg and a persistent woody-amber fragrance note.

EXAMPLE III A 3-liter reaction flask is charged with 800 g of 1,5,9- trimethyl cyclododecatriene-1,5 ,9 and the mass is cooled to 0C with good stirring. A previously prepared solution of 563 g. of BF -etherate and 457 g. of acetic anhydride is added at 0 to 5C over a period of 30 minutes. The mass is stirred for another 30 minutes at 0 to 5C and is then poured onto 1,500 g of an ice-water mixture containing 200 ml toluene. The separated oil layer is washed consecutively with equal volumes of water, 5 percent NaOH, and water and the solvent stripped off.

The residual oil weighs 908 g. Fractionation yields 240 g of recovered hydrocarbon and g of product testing 93.3 percent as C ketone by oximation and having a boiling point of l47-l66C at 2.5 mm Hg, a woody-amber fragrance, the IR and NMR spectra of FIGS. 1 and 2, respectively, a molecular weight of 246 (confirmed by mass spectrometry on a GLC trapped sample) and singly ionized fragments having m/e ratios of 43, 41, 39, 55,81, 53, 42, 59, 95, and 137.

EXAMPLE IV A two-liter reaction flask equipped with a stirrer, thermometer, addition funnel, reflux condenser, and drying tube is charged with the following materials:

900 g. of Trimethyl cyclododecatriene g. of Acetic anhydride.

With stirring and cooling to maintain the temperature at 25C is added a solution of 10 grams of BF -etherate and 180 g. acetic anhydride over a period of 20 minutes. The mixture is stirred at room temperature for another three hours, after which 100 ml of toluene and 500 ml of water are added.

The organic layer is separated and washed once with 300 ml of percent NaOH and then with 300 ml of salt solution. The solvent is stripped off to yield 946 g of crude product. Fractionation gives 486 g of recovered starting trimethyl cyclododecatriene and 243 g of acylated product (ketone) having a boiling range of ll8l26C at 1 mm Hg. The yield is 59 percent by weight (based on trimethyl cyclododecatriene utilized in the reaction). The ketone has a woody-amber fragrance note.

EXAMPLE V A 2-liter reaction flask equipped with a stirrer, thermometer, reflux condenser, addition funnel and drying tube is charged with 900 g of trimethyl cyclododecatriene, 250 g of acetic anhydride, and 45 g of zinc chloride. The reaction mixture is stirred and heated at 70C for one hour and then is poured into 1,100 ml of water and 100 ml of toluene. The oil layer is separated and the aqueous layer extracted with toluene. The combined organic material is washed with 100 ml of 5 percent aqueous sodium hydroxide solution and then with water, and the solvent stripped off to obtain 829 g of crude product. Fractionation gives 542 g of recovered trimethyl cyclododecatriene and 223 g of ketonic acylated product having a woody-amber fragrance note.

EXAMPLE VI To a mixture of 900 g of trimethyl cyclododecatriene and 500 g of propionic anhydride, cooled to C, is added dropwise '25 g of stannic chloride over a period of 1 hour while maintaining the temperature at l8-20C. The mixture is stirred for another 2 hours at -25C after the addition is completed and then is worked up as in Example IV.

The crude product is fractionated to yield 488 g of recovered hydrocarbon and 220 g of acylated product having a boiling range of 1 36 160C 'at 1.7 mm Hg and a woody-amber fragrance note. GLC (gas liquid phase chromatography) indicates a mixture of isomers, IR indicates the presence of a nonconjugated carbonyl, and mass spectroscopy indicates a molecular weight of 260.

The ketone so produced can be represented as follows:

CH3CH1C=O CH3 CHJCHZC O %CH2 0 CH; cm on;

EXAMPLE VII The crude product is fractionatedto yield 657 g recovered hydrocarbon and 146 g of acylated product having a woody-amber fragrance and a boiling range of 130135C at 2.2 mm Hg. GLC indicates a mixture of isomers. The IR spectrum, shown in FIG.v 7 as obtained on a Perkin-Elmer Model 21 instrument, indicates the presence of a nonconjugated carbonyl.

VIH

To a mixture of 900 g of tetrahydro 1,5,9-trimethyl cyclododecatrienes (from addition of two moles of hydrogen to trimethyl cyclododecatriene using Raney nickel as a catalyst at 60C and 250 lbs. pressure) and 180 g of acetic anhydride is added dropwise a solution of 10 g of BF -etherate and 180 g of acetic anhydride over a period of 20 minutes while maintaining the temperature at 25C. After the addition is completed, the material is held 3 hours at 25C, and thereaction mass is worked up as in Example IV.

The crude product is fractionated to give 567 g recovered hydrocarbon and 81 g of acylated product having a woody-amber fragrance and a boiling range of l28132C at 1.5 mm Hg. GLC indicates a mixture of isomers. The IR spectrum, shown in FIG. 8 as obtained on a Perkin-Elmer Model 21 instrument, indicates the presence of a nonconjugated carbonyl.

EXAMPLE IX Into a one-liter stainless steel stirred autoclave is placed 40 g of the ketonic product of Example I11, 125 g isopropanol, and 5 g Raney nickel. The mixture is bydrogenated at 500 psi and 100C to an uptake of one mole of H The catalyst is filtered and the solvent stripped off.

The residual oil which tests percent as C ketone by oximation is fractionated using a small Vigreux column to obtain materials havinga boiling range of l25-135C at 0.4 mm Hg, GLC indicates a mixture of isomers. IR indicates a nonconjugated carbonyl (5.83p.) plus a small amount of alcohol. The product has a woody-amber odor and the IR spectrum shown in FIG. 3, as obtained with a Perkin-Elmer Model 21 instrument.

EXAMPLE X In an analogous fashion to Example IX, 40 g of ketonic product of Example IV is hydrogenated to an uptake of two moles of hydrogen. The crude product is distilled at ll9126C at 0.6 mm Hg. GLC indicates a mixture of isomers. IR indicates a nonconjugated ketone. The product has a woody-amber fragrance and the IR spectrum shown in FIG. 4.

EXAMPLE XI In an analogous fashion to Example IX, 40 g of ketonic product of Example 111 is hydrogenated to an uptake of 3 moles of hydrogen. The crude product is distilled at 1l5l30C at 0.8 mm Hg. GLC indicates a mixture of isomers. IR analysis indicates a nonconjugated ketone. The distilled product has a woody-amber fragrance and the IR spectrum shown in FIG. 5, as obtained on a Perkin-Elmer Model 21 instrument.

EXAMPLE XII Into a 500 ml reaction vessel equipped with stirrer, thermometer, and reflux condenser, the following ingredients are added:

200 ml Anhydrous methyl alcohol 10 g Sodium methylate 50 g of Product of Example IV. The reactor contents are then heated to reflux (68C) for a period of 6 hours. To the reaction vessel is added the following:

200 ml of Water 10 ml of Acetic acid 50 ml of Toluene After separation the organic layer is washed once with water and the toluene is stripped off. The crude product weighing 40 g is distilled at 1 l7l23C at a pressure of 0.6 mm Hg. The yield of product is about 39 g. This product has a camphory woody-amber fragrance and the IR spectrum shown in FIG. 6, as obtained on a Perkin-Elmer Model 21 instrument. It is comprised of ketone having the structural formula "amass" or Joni EXAMPLE XIII A mixture of 10 grams of acetic anhydride and 6 grams of ferric chloride is prepared. A 500 ml reaction vessel is charged with l grams of l,5,9-trimethyl cyclododecatriene-l,5,9 and 35 grams of acetic anhydride. While maintaining the temperature of the reaction vessel at l025C, the acetic anhydride-ferric chloride mixture is added to the reaction mass over 8 hours. At the end of the 8-hour addition period, the reaction mass is mixed with 100 ml of water and 50 ml of toluene.

The reaction mass is then transferred to a separatory funnel and washed with 100 ml of percent aqueous sodium hydroxide solution and 200 ml of water. The organic layer is separated, and this organic layer is then stripped by a flash distillation to obtain 100 grams of product.

This product has the same properties as the product of Example [1].

EXAMPLE XIV l,5,9-Trimethyl cyclododecatriene-l 5.10 is prepared by reacting an equimolar mixture of piperylene and isoprene in a benzene reaction medium using a catalyst mixture comprising chromyl chloride and triethyl aluminum at a temperature of from 4550C. After destroying the catalyst, the mixture of these materials is distilled and the product recovered at a vapor temperature of 8493C at l.4 mm Hg.

A one-liter reaction flask fitted with a stirrer, thermometer and addition funnel is charged with 128 grams of the above trimethyl cyclododecatrienes produced by the trimerization of piperylene-isoprene mixtures, and 50 grams of acetic acid anhydride. A solution is then prepared containing 2.4 grams boron trifluoride diethyl ether and I0 grams of acetic anhydride. This solution is also charged into the one-liter reaction flask.

The reaction mass is stirred for 4% hours at 25C. The mass is then added to 50 ml of IO percent aqueous sodium chloride solution and 50 ml of toluene. The organic layer is separated from the aqueous phase and is washed with one volume of 5 percent aqueous sodium hydroxide solution until the mixture reaches pH 6. The organic layer is then washed with one volume of satu- 5 rated aqueous sodium chloride solution. The washed product is distilled at l C at 0.4 mm Hg to recover the ketones according to this invention. The ketones have the following structures 7 10 CH3C=O CH3 (II-130:0 CH2 l5 CH3 CH3 CH3 CH3 These structures are confirmed by infra-red and NMR analysis. The product has an excellent amber-woody fragrance character similar to that of the product of Example I.

EXAMPLE XV The following composition is prepared: Ingredient Amount (grams) Cassia absolute 6O Methyl ionone 60 Jasmin extra 80 Nemli oil. bigarade 60 Patchouli oil 60 Vanillin 60 Violet perfume base 60 The distilled acylate of Example l 60 Lemon oil 80 Rose geranium oil 120 Lavender oil. French I20 Sweet orange oil 80 Musk extract. 3% 5t) Civet extract, 3% 50 I000 The foregoing blend is tested and found to have the same desirable characteristics of richness and persistence provided by the very expensive vetivert oil and further posseses a novel woody, amber-like quality. The acylated material of Example I thus can substitute for or replace traditional materials such as sandalwood, vetivert, and patchouli.

Excellent results in the foregoing perfume compositions are also obtained utilizing the acylates prepared in Examples II to XIV in lieu of, or in admixture with, the acylate of Example I. Mixtures of these materials can also be used to good advantage in the perfume composition of Example XIII and other perfume and fragrance-modifying compositions.

Those skilled in the art will appreciate that the novel ketones prepared according to the present invention can further be treated to provide derivatives according to known reactions, and accordingly these ketones can be used as intermediates in the preparation of other CH: I CH:

3. A perfume mixture as defined in claim 1 wherein said ketone has the formula mo ceo H CH:

4. A perfume mixture as defined in claim 1 wherein said ketone has the formula 5. A process for modifying the fragrance properties of a composition which comprises adding an effective amount of a monocyclic alkyl ketone having the formula CH3 C 3 wherein R is a lower alkyl group having up to six carbon atoms, R is methyl or methylene, said ketone having from zero to three non-conjugated carbon-carbon double bonds to a composition.

6. A process as defined in claim 5 wherein said ketone has the formula CH3 CH3 7. A process as defined in claim 5 wherein said ketone has the formula HaC- 0:0 CH3 8. A process as defined in claim 5 wherein said ketone has the formula NIT D STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 I 816, 349 hated June 11 19 74 Inventor(s) HN B- It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In The Title; correct the spelling of PERFU I E" 7 Col. 4, line 63, after "at l7O8cm strike lines 65 through col. 5 line 2 "l,35Ocm and insert in. lieu thereof C=C-H bands at 1660 and 830 cm' and a I band at 1350cm' Col. 6, line 12; col. 7, line 10, col. 7, line 57, and OL-a, line 31; each occurrence correct the formul'ato read:

In each of col. 7,' line 15, and col. 8, line 35, change I 7 I II C 1 I I C ll Col. 8, line 50, change "CH t 3..-

Col. 10, lines 30 to 37, correct the formula to read:

,cH c=o CH Patent No. Dat d June 11, 1974 Inventor(s) JOHN HALL It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 16, lines 10 11017, correct the second formula to read:

(SEAL) Attest:

McCOY M. mason JR. Attesting Officer c. MARSHALL DANN.

Commissioner of Patents. 

2. A perfume mixture as defined in claim 1 wherein said ketone has the formula
 3. A perfume mixture as defined in claim 1 wherein said ketone has the formula
 4. A perfume mixture as defined in claim 1 wherein said ketone has the formula
 5. A process for modifying the fragrance properties of a composition which comprises adding an effective amount of a monocyclic alkyl ketone having the formula
 6. A process as defined in claim 5 wherein said ketone has the formula
 7. A process as defined in claim 5 wherein said ketone has the formula
 8. A process as defined in claim 5 wherein said ketone has the formula 